Late transition metal catalysts for olefin oligomerizations

ABSTRACT

A series of novel late transition metal catalysts for olefin oligomerization have been invented. The catalysts demonstrate high activity and selectivity for linear α-olefins.

CLAIM FOR PRIORITY

This application is a divisional of U.S. Ser. No. 10/693,584, filed Oct.24, 2003 which claims priority from U.S. Ser. No. 60/421,359 filed Oct.25, 2002 and U.S. Ser. No. 60/421,486 filed Oct. 25, 2002.

TECHNICAL FIELD

This document relates to late transition metal catalysts for olefinoligomerizations and to methods for making and using these catalysts.

BACKGROUND OF THE INVENTION

Alpha-olefins, especially those containing 6 to 20 carbon atoms, areimportant items of commerce. They are used as intermediates in themanufacture of detergents, as monomers (especially in linear low-densitypolyethylene), and as intermediates for many other types of products.Consequently, improved methods of making these compounds are desired.Especially desired, is a process capable of making a range of linearα-olefins such as 1-butene and 1-hexene.

Most commercially produced α-olefins are made by the oligomerization ofethylene, catalyzed by various types of compounds, see for instance B.Elvers, et al., Ed. Ullmann's Encyclopedia of Industrial Chemistry, Vol.A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p. 243-247 and275-276, and B. Cornils, et al., Ed., Applied Homogeneous Catalysis withOrganometallic Compounds, A Comprehensive Handbook, Vol. 1, VCHVerlagsgesellschaft mbH, Weinheim, 1996, p. 245-258. The major types ofcommercially used catalysts are alkylaluminum compounds, certainnickel-phosphine complexes, and a titanium halide with a Lewis acid suchas AlCl₃. In all of these processes, significant amounts of branchedinternal olefins and diolefins are produced. Since in most instancesthese are undesirable and often difficult to separate, these byproductsare avoided commercially.

SUMMARY

Invention catalyst systems, suitable for solution- or slurry-phaseoligomerization reactions to produce α-olefins, comprise a Group-8, -9,or -10 transition metal component (catalyst precursor) and an activator.Invention catalyst precursors can be represented by the general formula:

where M is a Group-8, -9, or -10 transition metal, especially Fe, Co andNi; N is nitrogen; P is phosphorus; Y is a hydrocarbyl bridge in whichfour or more carbon atoms connect between the nitrogen and phosphorusatoms; R¹, R², R³ and R⁴ are independently hydrocarbyl radicals such asC₁-C₄₀ aliphatic radicals, C₃-C₄₀ alicyclic radicals, C₆-C₄₀ aromaticradicals or combinations of these; X is independently a hydride radical,a hydrocarbyl radical, or hydrocarbyl-substituted organometalloidradical; or two X's are connected and form a 3 to 50 atom metallacyclering. When Lewis-acid activators such as methylalumoxane, aluminumalkyls, alkylaluminum alkoxides or alkylaluminum halides that arecapable of donating an X ligand, as described above, to the transitionmetal component are used, or when the ionic activator is capable ofextracting X, one or more X, which may optionally be bridged to oneanother, may additionally be independently selected from a halogen,alkoxide, aryloxide, amide, phosphide or other anionic ligand, providedthat the resulting activated catalyst contains as least one M-H or M-Cbond into which an olefin can insert.

DEFINITIONS

The term “hydrocarbyl radical” is sometimes used interchangeably with“hydrocarbyl” throughout this document. For purposes of this disclosure,“hydrocarbyl radical” encompasses C₁-C₅₀ radicals. These radicals can belinear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.Thus, the term “hydrocarbyl radical”, in addition to unsubstitutedhydrocarbyl radicals, encompasses substituted hydrocarbyl radicals,halocarbyl radicals, and substituted halocarbyl radicals, as these termsare defined below.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR″₂, OR″, PR″₂, SR″, BR″₂, SiR″₃, GeR″₃ and the like or whereat least one non-hydrocarbon atom or group has been inserted within thehydrocarbyl radical, such as O, S, NR″, PR″, BR″, SiR″₂, GeR″₂, and thelike, where R″ is independently a hydrocarbyl or halocarbyl radical. Thefunctional group can be an organometalloid radical.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen orhalogen-containing group (e.g. F, Cl, Br, I).

Substituted halocarbyl radicals are radicals in which at least onehydrocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR″₂, OR″, PR″₂, SR″, BR″₂, SiR″₃, GeR″₃and the like or where at least one non-carbon atom or group has beeninserted within the halocarbyl radical such as O, S, NR″, PR″, BR″,SiR″₂, GeR″₂, and the like where R″ is independently a hydrocarbyl orhalocarbyl radical provided that at least one halogen atom remains onthe original halocarbyl radical. The functional group can be anorganometalloid radical.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl,octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl,tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl,nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl,tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl,nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl,tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl,nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl,tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl,nonacosynyl, or triacontynyl isomers. For this disclosure, when aradical is listed it indicates that radical type and all other radicalsformed when that radical type is subjected to the substitutions definedabove. Alkyl, alkenyl and alkynyl radicals listed include all isomersincluding where appropriate cyclic isomers, for example, butyl includesn-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (andanalogous substituted cyclopropyls); pentyl includes n-pentyl,cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,and neopentyl (and analogous substituted cyclobutyls and cyclopropyls);butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls).

The transition metal component can also be described as comprising atleast one ancillary ligand that stabilizes the oxidation state of themetal. Ancillary ligands serve to enforce the geometry around the metalcenter. In this disclosure, ancillary ligands have a backbone thatcomprises nitrogen and phosphorus bridged to each other by at least 4atoms.

For purposes of this disclosure, oligomers include about 2-75 mer units.A mer is defined as a unit of an oligomer or polymer that originallycorresponded to the olefin that was used in the polymerization reaction.For example, the mer of polyethylene would be ethylene.

Abstractable ligands are ligands that are removed from the catalystprecursor to activate it. They are sometimes assigned the label X inthis disclosure. X are independently hydride radicals, hydrocarbylradicals, or hydrocarbyl-substituted organometalloid radicals; or twoX's are connected and form a 3-to-50-atom metallacycle ring. WhenLewis-acid activators such as methylalumoxane, aluminum alkyls,alkylaluminum alkoxides or alkylaluminum halides that are capable ofdonating an X ligand, as described above, to the transition metalcomponent are used, or when the ionic activator is capable of extractingX, one or more X, which may optionally be bridged to one another, mayadditionally be independently selected from a halogen, alkoxide,aryloxide, amide, phosphide or other anionic ligand, provided that theresulting activated catalyst contains as least one M-H or M-C connectionin which an olefin can insert.

In some structures throughout this specification the ligand-metalconnection is drawn with an arrow indicating that the electronsoriginally came from the ligand. At other times, connection is shown bydrawing a solid line. One of ordinary skill in the art recognizes thatthese depictions are interchangeable.

C₆F₅ is pentafluorophenyl or perfluorophenyl.

For purposes of this document, the term “comprising” is interchangeablewith “including”.

DETAILED DESCRIPTION

In one embodiment of this invention, the catalyst precursor can berepresented by the following formula:

where M, N, P, R¹, R², R³, R⁴ and X are defined above, and R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, and R¹² are independently hydrogen, fluorine, orC₁-C₂₀ hydrocarbyl radicals. The organic group connecting between N andP takes the place of Y, the hydrocarbyl bridge.

In other invention embodiments, R¹ and R² are independently C₁-C₁₂hydrocarbyl radicals, C₁-C₆ hydrocarbyl radicals, or methyl radicals. Inthese or other embodiments, R³ and R⁴ are independently C₆-C₂₀hydrocarbyl radicals, C₆-C₁₂ hydrocarbyl radicals, aromatic radicals,cyclohexyl radicals, or phenyl radicals.

Specific, invention catalyst precursor examples are illustrated by thefollowing formula where some components are listed in Table 1. For Y,alkylenes are diradicals and include all isomers of bridge length 4 orgreater, for example, hexylene includes 1,6-hexylene, 2,5-hexylene,2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methyl-1,5-pentylene,1,5-hexylene, 3,6-hexylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene,4-ethyl-1,4-butylene, and 1,4-hexylene. To illustrate members of thetransition metal component, select any combination listed in Table 1.For example, by choosing the first row components, the transition metalcompound would be1-(N,N-dimethylamino)-4-(P,P-dimethylphosphino)butylene nickeldichloride. By selecting a combination of components from Table 1, anexample would be2-(N,N-dimethlamino)-2′-(P,P-dicyclohexylphosphino)biphenyl nickeldibromide. Any combination of components may be selected.

R¹, R², R³, and R⁴ Y X¹ and X² M Methyl Butylene chloride nickel EthylPentylene bromide iron Propyl Hexylene iodide cobalt Butyl Heptylenemethyl palladium Pentyl Octylene ethyl platinum Hexyl Nonylene propylruthenium Heptyl Decylene butyl osmium Octyl Undecylene pentyl rhodiumNonyl Dodecylene hexyl iridium Decyl Tridecylene heptyl UndecylTetradecylene octyl Dodecyl Pentadecylene nonyl Tridecyl Hexadecylenedecyl Tetradecyl Heptadecylene undecyl Pentadecyl Octadecylene dodecylHexadecyl Nonadecylene tridecyl Heptadecyl Eicosylene tetradecylOctadecyl Heneicosylene pentadecyl Nonadecyl Docosylene hexadecylEicosyl tricosylene heptadecyl Heneicosyl tetracosylene octadecylDocosyl pentacosylene nonadecyl Tricosyl hexacosylene eicosyl Tetracosylheptacosylene heneicosyl Pentacosyl octacosylene docosyl Hexacosylnonacosylene tricosyl Heptacosyl triacontylene tetracosyl Octacosylcyclohexylene pentacosyl Nonacosyl cyclooctylene hexacosyl Triacontylcyclodecylene heptacosyl Ethenyl cyclododecylene octacosyl Propenyl2,2′-biphenyl nonacosyl Butenyl butenylene triacontyl Pentenylpenentylene hydride Hexenyl hexenylene phenyl Heptenyl heptenylenebenzyl Octenyl octenylene phenethyl Nonenyl nonenylene tolyl Decenyldecenylene methoxy Undecenyl undecenylene ethoxy Dodecenyl dodecenylenepropoxy Ethynyl hexynylene butoxy Propynyl heptynylene dimethylaminoButynyl octynylene diethylamino Pentynyl nonynylene methylethylaminoHexynyl decynylene phenoxy Heptynyl undecynylene benzoxy Octynyldodecynylene allyl Nonynyl butadienylene 1,1-dimethyl allyl Decynylpentadienylene 2-carboxymethyl allyl Undecynyl hexadienyleneacetylacetonate Dodecynyl heptadienylene 1,1,1,5,5,5-hexa-fluoroacetylacetonate Phenyl octadienylene 1,1,1-trifluoro-acetylacetonate Benzyl nonadienylene 1,1,1-trifluoro-5,5-di-methylacetylacetonate Phenethyl decadienylene Tolyl undecadienylene bothX¹ and X² Cyclobutyl dodecadienylene catecholate Cyclopentylhexatrienylene 3,5-dibutylcatecholate Cyclohexyl octatrienylene3,6-dibutylcatecholate Cycloheptyl decatrienylene 3,6-dibutyl-4,5-dimethoxycatecholate Cyclooctyl dodecatrienylene 3,6-dibutyl-4,5-dichlorocatecholate Cyclononyl 3,6-dibutyl-4,5- dibromocatecholateCyclodecyl 1,3-propylene Cyclododecyl 1,4-butylene

R³ and R⁴ can further independently be defined as one of the followingsubstituents:

where R′ are independently, hydrogen or C₁-C₅₀ hydrocarbyl radicals.Additionally, any two adjacent R′ may independently be joined to form asaturated or unsaturated cyclic structure.

Y can further be defined as one of the following bridging groups:

where R′ is as defined above, A is a non-hydrocarbon atom or group (i.e.C═O, C═S, O, S, SO₂, NR*, PR*, BR*, SiR*₂, GeR*₂ and the like where R*is independently a hydrocarbyl or halocarbyl radical), E is a Group-14element including carbon, silicon and germanium, x is an integer from 1to 4, and y is an integer from 0 to 4.

Common activators are useful with this invention: alumoxanes, such asmethylalumoxane, modified methylalumoxane, ethylalumoxane and the like;aluminum alkyls such as trimethyl aluminum, triethyl aluminum,triisopropyl aluminum and the like; alkyl aluminum halides such asdiethyl aluminum chloride and the like; and alkylaluminum alkoxides.

The alumoxane component useful as an activator typically is anoligomeric aluminum compound represented by the general formula(R″—Al—O)_(n), which is a cyclic compound, or R″(R″—Al—O)_(n)AlR″₂,which is a linear compound. In the general alumoxane formula, R″ isindependently a C₁-C₂₀ alkyl radical, for example, methyl, ethyl,propyl, butyl, pentyl, isomers thereof, and the like, and “n” is aninteger from 1-50. Most preferably, R″ is methyl and “n” is at least 4.Methylalumoxane and modified methylalumoxanes are most preferred. Forfurther descriptions see, EP 279586, EP 561476, WO94/10180 and U.S. Pat.Nos. 4,665,208, 4,908,463, 4,924,018, 4,952,540, 4,968,827, 5,041,584,5,103,031, 5,157,137, 5,235,081, 5,248,801, 5,329,032, 5,391,793, and5,416,229.

The aluminum alkyl component useful as an activator is represented bythe general formula R″AlZ₂ where R″ is defined above, and each Z isindependently R″ or a different univalent anionic ligand such as halogen(Cl, Br, I), alkoxide (OR″) and the like. Most preferred aluminum alkylsinclude triethylaluminum, diethylaluminum chloride, triisobutylaluminum,tri-n-octylaluminum and the like.

When alumoxane or aluminum alkyl activators are used, thecatalyst-precursor-to-activator molar ratio is from about 1:1000 to10:1; alternatively, 1:500 to 1:1; or 1:300 to 1:10.

Additionally, discrete ionic activators such as [Me₂PhNH][B(C₆F₅)₄],[Bu₃NH][BF₄], [NH₄][PF₆], [NH₄][SbF₆], [NH₄][AsF₆], [NH₄][B(C₆H₅)₄] orLewis acidic activators such as B(C₆F₅)₃ or B(C₆H₅)₃ can be used, ifthey are used in conjunction with a compound capable of alkylating themetal such as an alumoxane or aluminum alkyl. Discrete ionic activatorsprovide for an activated catalyst site and a relatively non-coordinating(or weakly coordinating) anion. Activators of this type are well knownin the literature, see for instance W. Beck., et al., Chem. Rev., Vol.88, p. 1405-1421 (1988); S. H. Strauss, Chem. Rev., Vol. 93, p. 927-942(1993); U.S. Pat. Nos. 5,198,401, 5,278,119, 5,387,568, 5,763,549,5,807,939, 6,262,202, and WO93/14132, WO99/45042 WO01/30785 andWO01/42249.

Invention catalyst precursors can also be activated with cocatalysts oractivators that comprise non-coordinating anions containingmetalloid-free cyclopentadienide ions. These are described in U.S.Patent Publication 2002/0058765 A1, published on 16 May 2002.

When a discrete ionic activator is used, thecatalyst-precursor-to-activator molar ratio is from 1:10 to 1.2:1; 1:10to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1.2:1; 1:5 to 10:1; 1:5 to 2:1;1:5 to 3:1; 1:5 to 5:1.

The catalyst-precursor-to-alkylating-agent molar ratio is from 1:10 to10:1; 1:10 to 2:1; 1:10 to 25:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 10:1;1:2 to 2:1; 1:2 to 25:1; 1:2 to 3:1; 1:2 to 5:1; 1:25 to 10:1; 1:25 to2:1; 1:25 to 25:1; 1:25 to 3:1; 1:25 to 5:1; 1:3 to 10:1; 1:3 to 2:1;1:3 to 25:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to25:1; 1:5 to 3:1; 1:5 to 5:1.

The catalyst systems of this invention can additionally be prepared bycombining in any order, the bidentate ligand:

where N, P, Y, R¹, R², R³ and R⁴ are as previously defined and aGroup-8, -9, or -10 halide salt which may optionally be coordinated bysolvent (for example NiX₂ or NiX₂.MeOCH₂CH₂OMe where X=Cl, Br or I) inan activator-compound solution (for example methylalumoxane dissolved intoluene). The reactants may be added in any order, or even essentiallysimultaneously.

Invention catalyst precursor solubility allows for the ready preparationof supported catalysts. To prepare uniform supported catalysts, thecatalyst precursor should significantly dissolve in the chosen solvent.The term “uniform supported catalyst” means that the catalyst precursoror the activated catalyst approach uniform distribution upon thesupport's accessible surface area, including the interior pore surfacesof porous supports.

Invention supported catalyst systems may be prepared by any methodeffective to support other coordination catalyst systems, effectivemeaning that the catalyst so prepared can be used for oligomerizingolefin in a heterogeneous process. The catalyst precursor, activator,suitable solvent, and support may be added in any order orsimultaneously. In one invention embodiment, the activator, dissolved inan appropriate solvent such as toluene is stirred with the supportmaterial for 1 minute to 10 hours. The total volume of the activationsolution may be greater than the pore volume of the support, but someembodiments limit the total solution volume below that needed to form agel or slurry (about 100-200% of the pore volume). The mixture isoptionally heated to 30-200° C. during this time. The catalyst can beadded to this mixture as a solid, if a suitable solvent is employed inthe previous step, or as a solution. Or alternatively, this mixture canbe filtered, and the resulting solid mixed with a catalyst precursorsolution. Similarly, the mixture may be vacuum dried and mixed with acatalyst precursor solution. The resulting catalyst mixture is thenstirred for 1 minute to 10 hours, and the catalyst is either filteredfrom the solution and vacuum dried, or vacuum or evaporation aloneremoves the solvent.

In another invention embodiment, the catalyst precursor and activatorare combined in solvent to form a solution. The support is then added tothis solution and the mixture is stirred for 1 minute to 10 hours. Thetotal volume of this solution may be greater than the pore volume of thesupport, but some embodiments limit the total solution volume below thatneeded to form a gel or slurry (about 100-200% pore volume). Theresidual solvent is then removed under vacuum, typically at ambienttemperature and over 10-16 hours. But greater or lesser times arepossible.

The catalyst precursor may also be supported in the absence of theactivator, in which case the activator is added to the liquid phase of aslurry process. For example, a solution of catalyst precursor is mixedwith a support material for a period of about 1 minute to 10 hours. Theresulting catalyst precursor mixture is then filtered from the solutionand dried under vacuum, or vacuum or evaporation alone removes thesolvent. The total volume of the catalyst precursor solution may begreater than the pore volume of the support, but some embodiments limitthe total solution volume below that needed to form a gel or slurry(about 100-200% of the pore volume).

Additionally, two or more different catalyst precursors may be placed onthe same support using any of the support methods disclosed above.Likewise, two or more activators may be placed on the same support.

Suitable solid particle supports typically comprise polymeric orrefractory oxide materials. Some embodiments select porous supports(such as for example, talc, inorganic oxides, inorganic chlorides(magnesium chloride)) that have an average particle size greater than 10μm. Some embodiments select inorganic oxide materials as the supportmaterial including Group-2, -3, -4, -5, -13, or -14 metal or metalloidoxides. Some embodiments select the catalyst support materials toinclude silica, alumina, silica-alumina, and their mixtures. Otherinorganic oxides may serve either alone or in combination with thesilica, alumina, or silica-alumina. These are magnesia, titania,zirconia, and the like. Lewis acidic materials such as montmorilloniteand similar clays may also serve as a support. In this case, the supportcan optionally double as the activator component. But additionalactivator may also be used.

As well know in the art, the support material may be pretreated by anynumber of methods. For example, inorganic oxides may be calcined, and/orchemically treated with dehydroxylating agents such as aluminum alkylsand the like.

Some embodiments select the carrier of invention catalysts to have asurface area of 10-700 m²/g, or pore volume of 0.1-4.0 cc/g, and averageparticle size from 10-500 μm. But greater or lesser values may also beused.

Invention catalysts may generally be deposited on the support at aloading level of 10-100 micromoles of catalyst precursor per gram ofsolid support; alternately from 20-80 micromoles of catalyst precursorper gram of solid support; or from 40-60 micromoles of catalystprecursor per gram of support. But greater or lesser values may be used.Some embodiments select greater or lesser values, but require that thetotal amount of solid catalyst precursor does not exceed the support'spore volume.

Additionally, oxidizing agents may be added to the supported orunsupported catalyst as described in WO 01/68725.

Process

In the invention oligomerization processes, the process temperature maybe −100° C. to 300° C., −20° C. to 200° C., or 0° C. to 150° C. Someembodiments select ethylene oligomerization pressures (gauge) from 0kPa-35 MPa or 500 kPa-15 MPa.

The preferred and primary feedstock for the oligomerization process isthe α-olefin, ethylene. But other α-olefins, including but not limitedto propylene and 1-butene, may also be used alone or combined withethylene.

Invention oligomerization processes may be run in the presence ofvarious liquids, particularly aprotic organic liquids. The homogeneouscatalyst system, ethylene, α-olefins, and product are soluble in theseliquids. A supported (heterogeneous) catalyst system may also be used,but will form a slurry rather than a solution. Suitable liquids for bothhomo- and heterogeneous catalyst systems, include alkanes, alkenes,cycloalkanes, selected halogenated hydrocarbons, aromatic hydrocarbons,and in some cases, hydrofluorocarbons. Useful solvents specificallyinclude hexane, toluene, cyclohexane, and benzene.

Also, mixtures of α-olefins containing desirable numbers of carbon atomsmay be obtained. Factor K from the Schulz-Flory theory (see for instanceB. Elvers, et al., Ed. Ullmann's Encyclopedia of Industrial Chemistry,Vol. A13, VCH Verlagsgesellschaft mbH, Weinheim, 1989, p. 243-247 and275-276) serves as a measure of these α-olefins' molecular weights. Fromthis theory,K=n(C_(n+2) olefin)/n(C_(n) olefin)where n(C_(n) olefin) is the number of moles of olefin containing ncarbon atoms, and n(C_(n+2) olefin) is the number of moles of olefincontaining n+2 carbon atoms, or in other words the next higher oligomerof C_(n) olefin. From this can be determined the weight (mass) fractionsof the various olefins in the resulting product. The ability to varythis factor provides the ability to choose the then-desired olefins.

Invention-made α-olefins may be further polymerized with other olefinsto form polyolefins, especially linear low-density polyethylenes, whichare copolymers containing ethylene. They may also be homopolymerized.These polymers may be made by a number of known methods, such asZiegler-Natta-type polymerization, metallocene catalyzed polymerization,and other methods, see for instance WO 96/23010, see for instance Angew.Chem., Int. Ed. Engl., vol. 34, p. 1143-1170 (1995); European PatentApplication, 416,815; and U.S. Pat. No. 5,198,401 for information aboutmetallocene-type catalysts, and J. Boor Jr., Ziegler-Natta Catalysts andPolymerizations, Academic Press, New York, 1979 and G. Allen, et al.,Ed., Comprehensive Polymer Science, Vol. 4, Pergamon Press, Oxford,1989, pp. 1-108, 409-412 and 533-584, for information aboutZiegler-Natta-type catalysts, and H. Mark, et al., Ed., Encyclopedia ofPolymer Science and Engineering, Vol. 6, John Wiley & Sons, New York,1992, p. 383-522, for information about polyethylene.

Invention-made α-olefins may be converted to alcohols by knownprocesses, these alcohols being useful for a variety of applicationssuch as intermediates for detergents or plasticizers. The α-olefins maybe converted to alcohols by a variety of processes, such as the oxoprocess followed by hydrogenation, or by a modified, single-step oxoprocess (the modified Shell process), see for instance B. Elvers, etal., Ed., Ullmann's Encyclopedia of Chemical Technology, 5th Ed., Vol.A18, VCH Verlagsgesellschaft mbH, Weinheim, 1991, p. 321-327.

A set of exemplary catalyst precursors is set out below. These are byway of example only and are not intended to list every catalystprecursor that is within the scope of the invention.

Several structures are shown along with their corresponding name.

EXAMPLES

The following examples are presented to illustrate the discussion above.Although the examples may be directed toward certain embodiments of thepresent invention, they do not limit the invention in any specific way.In these examples, certain abbreviations are used to facilitate thedescription. These include standard chemical abbreviations for theelements and certain, commonly accepted abbreviations, such as:Me=methyl, Ph=phenyl, Cy=cyclohexyl, MAO=methylalumoxane,COD=cyclooctadiene and DME=ethylene glycol dimethyl ether.

All preparations were performed under an inert nitrogen atmosphere usingstandard Schlenk or glovebox techniques, unless mentioned otherwise. Drysolvents (toluene, diethyl ether, pentane, methylene chloride) werepurchased as anhydrous solvents and further purified by passing themdown an alumina (Fluka) column. Ethylene (99.9%) was purchased from BOC(Surrey, United Kingdom).2-(N,N-dimethlamino)-2′-(dicyclohexylphosphino)biphenyl and2-(N,N-dimethlamino)-2′-(diphenylphosphino)biphenyl were purchased fromStrem Chemicals, Inc. Tetramethyltin, nickel(II) bromide ethylene glycoldimethylether complex, and dichloro(1,5-cyclooctadiene)palladium(II)were purchased from Aldrich Chemical Company. Deuterated solvents weredried with CaH and vacuum distilled prior to use.

Some compounds prepared are illustrated below:

Preparation of 2-(N,N-dimethlamino)-2′-(dicyclohexylphosphino)biphenylnickel dibromide (Compound 1)

CH₂Cl₂ (25 ml) was added to a Schlenk flask containing2-(N,N-dimethlamino)-2′-(dicyclohexylphosphino)biphenyl (2.00 g, 5.10mmol) and (DME)NiBr₂ (1.23 g, 4.0 mmol) in a dry box. A dark bluesolution formed immediately upon mixing. This solution was stirred for20 hours. Then, it was filtered and recrystallized from CH₂Cl₂/pentane.The product was washed three times with an additional 15 ml of pentaneand dried for 1 hour under vacuum. A blue powder was isolated in 49.0%yield. The product was soluble in CH₂Cl₂. ¹H NMR indicates that it isparamagnetic. Anal. Calcd for (C₂₆H₃₆NPBr₂Ni): C, 51.02%; H, 5.94%; N,2.29%; P, 5.06%. Found: C, 50.72%; H, 6.10%; N, 2.12%; P, 5.02%. The IR(cm⁻¹, KBr): 272, ν(Ni—Br). This compound has also been characterized byx-ray crystallography.

Preparation of 2-(N,N-dimethlamino)-2′-(diphenylphosphino)biphenylnickel dibromide (Compound 2)

CH₂Cl₂ (25 ml) was added to a Schlenk flask containing the2-(N,N-dimethlamino)-2′-(diphenylphosphino)biphenyl (2.00 g, 5.2 mmol)and (DME)NiBr₂ (1.30 g, 4.2 mmol) in a dry box. A green solution formedimmediately upon mixing. This solution was stirred for 20 hours. Then,it was filtered and recrystallized from CH₂Cl₂/pentane. The product waswashed three times with an additional 15 ml of pentane and dried for 1hour under vacuum. A green powder was isolated in 69.3% yield. Theproduct was soluble in CH₂Cl₂. ¹H NMR indicates that it is paramagnetic.Anal. Calcd for (C₂₆H₂₄NPBr₂Ni): C, 52.03%; H, 4.08%; N, 2.33%; P,5.16%. Found: C, 1.20%; H, 4.24%; N, 2.14%; P, 5.29%.

Preparation of 2-(N,N-dimethylamino)-2′-(dicyclohexylphosphino)biphenylpalladium methy chloride (Compound 3)

(COD)PdCl₂ (2.0 g, 7.0 mmol) was mixed with tetramethyltin (1.16 ml, 8.4mmol) in CH₂Cl₂ (50 ml) at room temperature. The mixture was stirredovernight until the bright yellow color of the precursor had vanished.The resulting mixture was filtered through Celite yielding a pale yellowsolution. The solvent was removed from the that solution, leaving behindan off-white solid, (COD)PdClMe, which was washed twice with diethylether and dried under vacuum. A solution of the white (COD)PdClMecomplex (0.775 g, 0.0029 mol dissolved in CH₂Cl₂) was reacted with2-(N,N-dimethlamino)-2′-(dicyclohexylphosphino)biphenyl (1.78 g, 0.0045mol). As a result, a light yellow palladium complex formed. ¹H NMR (250MHz, CD₂Cl₂, δ ppm): 0.88-2.94 m (22H, 2×C₆H₁₁); 1.06 d (3H, PdCH₃,J_(PH)=2.5 Hz); 2.87 s (6H, 2×CH₃); 6.75-7.68 m (8H, 2×C₆H₄). Anal.Calcd for (C₂₇H₃₉NPClPd): C, 58.91%; H, 7.16%; N, 2.55%; P, 5.63%.Found: C, 59.21%; H, 7.31%; N, 2.38%; P, 5.41%.

Oligomerization Reactions

Oligomerization reactions were run in 300 mL HastelloyC Parr reactorequipped with a mechanical stirrer. Catalyst (dissolved in 75 mltoluene) was added to the reactor under argon. Ethylene was added to thereactor at 100 psig, and then the reactor was vented to maintain anatmosphere of ethylene. Methylalumoxane solution (Albemarle, 30 wt % intoluene) was then cannulated in to the reactor. This process causedcatalyst activation to be completed in the presence of the monomer.After activation, the ethylene pressure was adjusted to the desiredvalue. It was attempted to maintain the reactor temperature at roomtemperature; but in cases where the exotherm was very large, higherreaction temperatures were reached. After the reaction had run for anhour, the reactor was cooled in an acetone/dry ice bath and vented. Thereaction was quenched with methanol. A sample of the product solutionwas analyzed by GC/MS after adding nonane as an internal standard. Inthe case of supported transition metal compounds, silica-loaded sampleswere prepared by adding a solution of the transition metal complex inmethylene chloride to silica followed by overnight drying of the silicaunder vacuu. MAO was added to the reactor solution prior to adding thesupported transition metal compound. The results of the oligomerizationreactions are tabulated below in Table 2.

TABLE 2 Oligomerization Examples Final Rxn C₂ Tempera- ActivityCatalyst^(a) (psig) ture (° C.) (mol C₂/mol Ni · hr) Product 1 820 40226,200 Linear C₄ to C₁₄ (K* = 0.60)^(b) 1 100 30 26,700 Primarily C₄and C₆ (linear) 1 800 25 155,000 Primarily C₄ and C₆ (linear)^(c) 2 80030 130,000 C₄ 2 100 30 8095 C₄ ^(a)0.0075 mmol of catalyst ^(b)*K isbased on C₁₄/C₁₂ molar ratio for all isomers. ^(c)After removing allvolatiles at room temperature under vacuum, traces of higher oligomerswere observed by NMR in the residue with 84 mol % of terminal olefins;GC/MS of the same residue showed C₁₆ to C₂₄ oligomers.

While certain representative embodiments and details have been shown toillustrate the invention, it will be apparent to skilled artisans thatvarious process and product changes from those currently disclosed maybe made without departing from this invention's scope. The appendedclaims define the invention's scope.

All cited patents, test procedures, priority documents, and other citeddocuments are fully incorporated by reference to the extent that thismaterial is consistent with this specification and for all jurisdictionsin which such incorporation is permitted.

Certain features of the present invention are described in terms of aset of numerical upper limits and a set of numerical lower limits. Thisspecification discloses all ranges formed by any combination of theselimits. All combinations of these limits are within the scope of theinvention unless otherwise indicated.

1. A polymerization process comprising contacting an alpha-olefin withan activator and a composition of matter with the following formula:

wherein M is a Group-8, -9, or -10 transition metal, excludingpalladium, N is nitrogen; P is phosphorus; R¹, R², R³, and R⁴ areindependently hydrocarbyl radicals; Y is a hydrocarbyl bridge comprisinga backbone wherein the backbone comprises a chain that is four or morecarbon atoms long; X is independently an abstractable ligand.
 2. Theprocess of claim 1 wherein R¹, R², R³, and R⁴ are independently selectedfrom C₁-C₄₀ hydrocarbyls.
 3. The process of claim 2 wherein R¹, R², R³,and R⁴ are independently selected from C₁-C₃₀ hydrocarbyls.
 4. Theprocess of claim 3 wherein R¹, R², R³, and R⁴ are independently selectedfrom methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl,decynyl, undecynyl, dodecynyl, phenyl, benzyl, phenethyl, tolyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl radicals.
 5. The process of claim 4wherein R¹, R², R³, and R⁴ are independently selected from methyl,ethyl, propyl, butyl, cyclohexyl, phenyl, tolyl, benzyl, and phenethyl.6. The process of claim 1 wherein X are independently hydride radicals;hydrocarbyl radicals; hydrocarbyl-substituted, organometalloid radicals;or two X's are connected to form a 3-to-50-atom metallacycle ring. 7.The process of claim 1 wherein X are independently halogen, alkoxide,aryloxide, amide, or phosphide radicals.
 8. The process of claim 7wherein X are independently chloride, bromide, iodide, methoxy, ethoxy,propoxy, butoxy, dimethylamino, diethylamino, methylethylamino, phenoxy,or benzoxy.
 9. The process of claim 6 wherein X are independentlyhalogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl,docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl,octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl, phenethyl, ortolyl.
 10. The process of claim 1 wherein X are independently allyl,1,1-dimethyl allyl, 2-carboxymethyl allyl, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals.
 11. Theprocess of claim 1 wherein M is selected from nickel, iron, cobalt,platinum, ruthenium, osmium, rhodium, and iridium.
 12. The process ofclaim 11 wherein M is selected from iron, nickel, and cobalt.
 13. Theprocess of claim 11 wherein Y is selected from butylene, pentylene,hexylene, heptylene, octylene, nonylene, decylene, undecylene,dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene,heptadecylene, octadecylene, nonadecylene, eicosylene, heneicosylene,docosylene, tricosylene, tetracosylene, pentacosylene, hexacosylene,heptacosylene, octacosylene, nonacosylene, triacontylene, cyclohexylene,cyclooctylene, cyclodecylene, cyclododecylene, biphenyl, butenylene,penentylene, hexenylene, heptenylene, octenylene, nonenylene,decenylene, undecenylene, dodecenylene, hexynylene, heptynylene,octynylene, nonynylene, decynylene, undecynylene, dodecynylene,butadienylene, pentadienylene, hexadienylene, heptadienylene,octadienylene, nonadienylene, decadienylene, undecadienylene,dodecadienylene, hexatrienylene, octatrienylene, decatrienylene, anddodecatrienylene radicals.
 14. The process of claim 13 wherein Y isbiphenyl.
 15. The process of claim 13 wherein Y has one of the followingformulas:

where (a) R′ are independently, hydrogen or C₁-C₅₀ hydrocarbyl radicals;(b) A is a non-hydrocarbon atom functional group; (c) E is a Group-14element; (d) x is an integer from 1 to 4; and (e) y is an integer from 0to
 4. 16. The process of claim 15 wherein A is selected from C═O, C═S,O, S, SO₂, NR*, PR*, BR*, SiR*₂, and GeR*₂ wherein R* is independently ahydrocarbyl or halocarbyl radical.
 17. The process of claim 1, whereinthe alpha-olefin is ethylene, propylene, 1-butene, or a mixture of anytwo or all three of ethylene, propylene, and 1-butene.
 18. Apolymerization process comprising the step of providing an activator andat least one composition of matter represented by the formula:

wherein (a) M is a Group-8, -9, or -10 transition metal, excludingpalladium, (b) N is nitrogen; (c) P is phosphorus; (d) R¹, R², R³, andR⁴ are independently hydrocarbyl radicals; (e) Y is a hydrocarbyl bridgecomprising a backbone wherein the backbone comprises a chain that isfour or more carbon atoms long; and (f) X is independently anabstractable ligand.
 19. The polymerization process of claim 1 whereinthe catalyst activity exceeds 8000 moles of ethylene per mole transitionmetal per hour.
 20. The polymerization process of claim 1 furthercomprising recovering a product comprising greater than 50 wt % oflinear C₄-C₁₄ α-olefins based on the total weight of polymerizedproduct.
 21. The polymerization process of claim 1 wherein the productcomprises greater than 80 wt % of linear C₄-C₁₄ α-olefins.
 22. Thepolymerization process of claim 21 wherein the product comprises greaterthan 50 wt % of linear C₄ and C₆ α-olefins.
 23. The polymerizationprocess of claim 22 wherein the product comprises greater than 80 mol %of linear C₄ and C₆ α-olefins.
 24. A polymerization process comprisingcontacting an alpha-olefin with a composition of matter comprising thereaction product of: (a) an activator; and (b) a catalyst precursor withthe following formula:

wherein (i) M is iron, nickel, cobalt, and palladium; (ii) N isnitrogen; (iii) P is phosphorus; (iv) R¹, R², R³, and R⁴ areindependently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl,undecenyl, dodecenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, phenyl,benzyl, phenethyl, tolyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl radicals;(v) Y is a hydrocarbyl bridge comprising a backbone wherein the backbonecomprises a chain that is four or more carbon atoms long; (vi) X areindependently abstractable ligands.
 25. The process of claim 24, whereinX are independently chloride, bromide, iodide, methoxide, ethoxide,dimethylamide, diethylethoxide, phenoxide, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl,hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hydride,phenyl, benzyl, phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy,dimethylamino, diethylamino, methylethylamino, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di-methylacetylacetonate radicals; or two X's areconnected to form a 3-to-40-atom metallacycle ring; and Y is selectedfrom butylene, pentylene, hexylene, heptylene, octylene, nonylene,decylene, undecylene, dodecylene, tridecylene, tetradecylene,pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene,eicosylene, heneicosylene, docosylene, tricosylene, tetracosylene,pentacosylene, hexacosylene, heptacosylene, octacosylene, nonacosylene,triacontylene, cyclohexylene, cyclooctylene, cyclodecylene,cyclododecylene, biphenyl, butenylene, pentenylene, hexenylene,heptenylene, octenylene, nonenylene, decenylene, undecenylene,dodecenylene, hexynylene, heptynylene, octynylene, nonynylene,decynylene, undecynylene, dodecynylene, butadienylene, pentadienylene,hexadienylene, heptadienylene, octadienylene, nonadienylene,decadienylene, undecadienylene, dodecadienylene, hexatrienylene,octatrienylene, decatrienylene, and dodecatrienylene radicals.
 26. Apolymerization process wherein the catalyst activity exceeds 8000 molesof ethylene per mole transition metal per hour comprising the step ofproviding at least one composition of matter comprising the reactionproduct of: (a) an activator; and (b) a catalyst precursor with thefollowing formula:

wherein (i) M is iron, nickel, cobalt, and palladium; (ii) N isnitrogen; (iii) P is phosphorus; (iv) R¹, R², R³, and R⁴ areindependently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl,undecenyl, dodecenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl,heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, phenyl,benzyl, phenethyl, tolyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl radicals;(v) Y is a hydrocarbyl bridge comprising a backbone wherein the backbonecomprises a chain that is four or more carbon atoms long; (vi) X areindependently abstractable ligands; and contacting said reaction productwith an alpha-olefin.
 27. A polymerization process wherein the catalystactivity exceeds 8000 moles of ethylene per mole transition metal perhour comprising the step of providing at least one composition of mattercomprising the reaction product of: (a) an activator; and (b) a catalystprecursor with the following formula:

wherein (i) M is from nickel, iron, cobalt, palladium, platinum,ruthenium, osmium, rhodium, and iridium; (ii) N is nitrogen; (iii) P isphosphorus; (iv) R¹, R², R³, and R⁴ are independently selected frommethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl,decynyl, undecynyl, dodecynyl, phenyl, benzyl, phenethyl, tolyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl radicals; (v) Y is a hydrocarbylbridge comprising a backbone wherein the backbone comprises a chain thatis four or more carbon atoms long; and (vi) X are independentlychloride, bromide, iodide, methoxide, ethoxide, dimethylamide,diethylethoxide, phenoxide, methyl, ethyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, hydride, phenyl, benzyl,phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy, dimethylamino,diethylamino, methylethylamino, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di- methylacetylacetonate radicals; or two X'sare connected to form a 3-to-40-atom metallacycle ring; and contactingsaid reaction product with an alpha-olefin.
 28. A polymerization processwherein the catalyst activity exceeds 8000 moles of ethylene per moletransition metal per hour comprising the step of providing at least onecomposition of matter comprising the reaction product of: (a) anactivator; and (b) a catalyst precursor with the following formula:

wherein (i) M is from nickel, iron, cobalt, palladium, platinum,ruthenium, osmium, rhodium, and iridium; (ii) N is nitrogen; (iii) P isphosphorus; (iv) R¹, R², R³, and R⁴ are independently selected frommethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, ethynyl,propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl,decynyl, undecynyl, dodecynyl, phenyl, benzyl, phenethyl, tolyl,cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,cyclononyl, cyclodecyl, cyclododecyl radicals; (v) Y is selected frombutylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene,undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene,hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene,heneicosylene, docosylene, tricosylene, tetracosylene, pentacosylene,hexacosylene, heptacosylene, octacosylene, nonacosylene, triacontylene,cyclohexylene, cyclooctylene, cyclodecylene, cyclododecylene, biphenyl,butenylene, pentenylene, hexenylene, heptenylene, octenylene,nonenylene, decenylene, undecenylene, dodecenylene, hexynylene,heptynylene, octynylene, nonynylene, decynylene, undecynylene,dodecynylene, butadienylene, pentadienylene, hexadienylene,heptadienylene, octadienylene, nonadienylene, decadienylene,undecadienylene, dodecadienylene, hexatrienylene, octatrienylene,decatrienylene, and dodecatrienylene radicals; and (vi) X areindependently chloride, bromide, iodide, methoxide, ethoxide,dimethylamide, diethylethoxide, phenoxide, methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl,hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hydride,phenyl, benzyl, phenethyl, tolyl, methoxy, ethoxy, propoxy, butoxy,dimethylamino, diethylamino, methylethylamino, acetylacetonate,1,1,1,5,5,5-hexa-fluoroacetylacetonate, 1,1,1-trifluoro-acetylacetonate,or 1,1,1-trifluoro-5,5-di- methylacetylacetonate radicals; or two X'sare connected to form a 3-to-40-atom metallacycle ring; and contactingsaid reaction product with an alpha-olefin.